Catalytic condensation of certain carbohydrates with aromatic hydrocarbons and haloaromatic compounds



United States Patent CATALYTIC CONDENSATION OF CERTAIN CAR- BOHYDRATES WITH ARONIATIC HYDROCAR- BONS AND HALOA-ROMATIC COMPOUNDS Carl B. Linn, Riverside, ]]l., assign'or, by mesne assignments, to Universal Oil Products Company, Des Plaines, 11]., a corporation of Delaware No Drawing. Application December 3, 1956 Serial No. 625,613

17 Claims. or. 260-618) This application is a continuation-in-part of my copending application Serial No. 441,167, filed July 2, 1954, which is a continuation-in-part of application Serial No. 215,627, filed March 14, 1951, both of said earlier applications being now abandoned.

This invention relates to a process for interacting compounds selected from the group consisting of aromatic hydrocarbons and haloaromatic compounds with certain carbohydrates. The process relates more particularly to the condensation of monosaccharides or simple sugars, naturally occurring desoxy-monosaccharides, omega-carboxy-monosaccharides, and'oligosaccharides or compound sugars with compounds selected from the group consisting of. aromatic hydrocarbons and haloaromatic compounds in'the presence of a Friedel-Crafts metal halide as the reaction catalyst.

An object of this invention is to produce organic materials suitable for use. per se or for use as intermediates in themanufacture .of detergents, pharmaceuticals, explosives, gel 1ingagents,'surface coatings, resins, plastici'z'ers, etc, by reacting a compound selected from the group'consisting of aromatic hydrocarbons and haloaromatic' compounds with certain carbohydrates, Some of the compounds produced in accordance with the process of thisinvention are not new. For example, certain socalled'mono-substituted desoxy-glycoses are described in U.S.P. 2,472,277. Some of these compounds formerly called aryl-substitutedvdesoxy-glycoses and now more properly named aryl-substituted-desoxy-alditols and" arylsubstituted-desoXy-ketitols are produced by the process ofthe present invention; Furthermore, the preparation of certain diaryl-desoxy-alditols is described in U.S.P. 2,472,- 276. Some of these compounds are also produced by the process of the present invention. That these compounds 'are not novel is shown in U.S.P. 2,460,803 wherein diaryl-desoXy-alditolsare claimed, among other compounds, asnovel compositions However, certain novel compo sitions of matter. and. new'compounds have been produced by the process of the present invention as'will be set forth hereinafter. Thus, the compounds produced by the' 'process of the present .invention can be described as b'othlold, and new ornoveli I I One embodiment of this invention relates to a process which comprises reacting a compound selected from the group consisting of aromatic hydrocarbons and haloaromatic compounds withacarbohydrate selected from the group consisting of'monosaccharides, naturally-occurringdesoxy-monosaccharides, omega carboxy monosaccharides, and oligo-saccharides in the presence of a catalyticamountof a Friedel-Crafts metal halide at reaction conditions of temperature and pressure to produce a compound selected from. the group consisting of an aryl-substituteddesoxyalditol, aryl-substituted desoxyketitol, a haloaryl substituted desoxy-alditol, and a haloaryl substituted-desoxy ketitol, and recovering said comndund; I

Another embodiment of this invention relates to a process which comprises reacting an'aromatic hydro- 2 carbon with a carbohydrate selected from the'group consisting of monosaccharides, naturally-occurring desoxymonosaccharides, omega-carboxy-monosaccharides, and oligosaccharides in the presence of a catalytic amount of aluminum chloride at atemperature offrom about room temperature to about C. and at a pressure offrom about atmospheric to about 1-00 pounds per square inch to produce a compound selected from the group consisting of an aryl-substituted-desoXy-alditol andan arylsubstituted-desoxy-ketitol, and recovering. said compound.

A still further embodiment of this invention relates to a process which comprises reacting a haloaromatic compound with a carbohydrate selected from the group consisting of a monosaccharide, naturally-occurring des-' oxy monosaccharides, omega-carboxy-monosaccharides, and oligosaccharides in the presence of a catalytic amount of aluminum chloride at (a temperature of from room temperature to about 100 C. and a pressure of from about atmospheric to about 100 pounds per square inch to produce a compound selected from the group consisting of haloaryl-substituted-desoXy-alditols and haloarylsubstituted-desoXy-ketitols, and recovering said compound.

A specific embodiment of this invention relatest'o a process which comprises reacting benzene with glucose in the presence of a catalytic amount of aluminum chloride at :a temperature of from about room temperature to about 100 C. and at a pressure of from atmospheric to about 100 pounds per square inch to produce a phenyl-- l-desoxy-glucitol, and recovering said compound.

Another specific embodiment of this invention relates to a process which comprises reacting toluene with glu cose in the presence of a catalytic amount of aluminum chloride at a temperature of from about room temperature to about 100 C. and at a pressure of from about atmospheric to about 100 pounds per square inchto produce a p-tolyl-l-desoxy-glucitol, and recovering said compound.

Still another-specificembodiment of this inventionre lates to a process which comprises reacting chlorobenzone with glucose in the presence of a catalytic amount of aluminum chloride at a temperature of from about room temperature to about 100 C. and ata pressure of from about atmospheric to about 100 pounds per square inch to produce a 4-chloro-phenyl-l-desoxy-gluci" tol, and recovering said compound.

A still further specific embodiment of this invention relates to a process which comprises 'reacting'toluene with' fructose in the presence of a catalytic amount of'alu'mi-' num chloride at a temperature of from about room tem-' perature-to about 100 C. andat apressure of from'about" atmospheric to about 100 pounds per square'inch to pro-" ducea p-tolyl-Z-desoXy-fructitol, and recovering said com pound.

Another specific embodiment of this invention relates" to a process which comprises reacting toluene withsucrose in the presence of a catalytic amount of aluminum chloride at a temperature of from about room tempera ture to about 100 C. and at a pressure of from about atmospheric to about 100 pounds per square inch to produce a compound selected from the group consisting of p-tolyl-l-desoxy-glucitol and a p-toly1-2-desoxy-fructi tol, and recoveringsaid compound.

I havefound that useful Water-insoluble reaction prod-' action has previously been extended to thereactionof aromatic hydrocarbons with certain carbohydrate derivatives, namely, the reaction of aromatic hydrocarbonswith polyacylglycosyl esters. This reaction as stated compounds which are produced by the process of the present invention. However, the polyacylglycosyl esters must first be prepared for use in the above-mentioned process. I have unexpectedly found that this prior formation of polyacylglycosyl halides and polyacylglycosyl acetates is not necessary and that certain carbohydrates, as for example in their naturally occurring states, may be directly reacted with aromatic hydrocarbons and hair)- aromatic compounds in a still further extension of the F-riedel-Crafts reaction. Prior to my discovery it has been considered necessary to protect the functional groups in sugars so that selective reactions could be obtained to yield ure compounds. I have found that such protection is unnecessary and that selective reactions are obtained without such prior protection and preparation of intermediate compounds prior to reaction with an aromatic hydrocarbon or haloaromatic compound. Thus, my discovery results in a further simplification of known processes and makes for more economical production of certain chemical compounds. My reactions may be carried out in steel equipment or in suitable apparatus such as glass or in other suitable apparatus lined with such inert materials as glass, ceramic materials, silver, copper, and certain allovs such as Monel metal, stainless steel, and the like. This reaction may be effected at tem eratures of from about C. to about 150 C. and preferably at temperatures of from about room temperature to about 100 C. While any of these reactions are conveniently carried out at substantially atmospheric pressure, it may be desirable in certain instances and with certain reactants to carry out the reaction at higher pressures up to 100 atmospheres or more, although pressures of greater than 100 pounds per square inch are seldom necessary. When utilizing pressure-withstanding equipment. it is convenient in most instances to operate the equipment utilized at the autogenous pressure generated by the reaction mixture contained therein.

It might be considered by some to be predictable that in the presence of a Friedel-Crafts type catalyst some kind of reaction should occur when a reaction mixture contains a carbohydrate and other organic compounds. However, it has unexpectedly been found that selective reaction takes place when certain carbohydrates are reacted with certain other organic compounds. This selective reaction results in high yields of pure compounds. As hereinabove stated, this unexpected and selective reaction takes place in the presence of a Friedel-Crafts catalyst when a carbohydrate selected from the group consisting of monosaccharides, naturally-occurring desoxymonosaccharides, omega-carboxy-monosaccharides, oligosaccharides are reacted with an aromatic hydrocarbon or a. haloaromatic compound. Suitable aromatic hydrocar-' bons which may be used as starting materials in the process of this invention include benzene, toluene, orthoxylene, meta-Xylene, para-xylene, ethylbenzene, orthoethyltoluene, meta-ethyltoluene, para-ethyltoluene, 1,2,3- trimethylbenzene, 1,2,4-trimethylbenzene, 1,3,5-trimethylbenzene. n-propyl benzene, cumene or isopropyl benzene, etc. Other suitable utilizable aromatic hydrocarbons include those with two or more aryl groups such as diohenyl diphenylmethane, triphenylmethane, fluorene, stilbene, etc., and aromatic hydrocarbons which contain condensed benzene rings including naphthalene, alpha-methylnaphthalene, beta-methylnaphthalene, ethylnaphthalene, anthracene, phenanthrene, naphthac ene, rubrene, etc. Alkylaromatic hydrocarbons in which the alkyl group contains more than 3 carbon atoms are also utilizable in the process of the present invention but not necessarily with equivalent results. This is due to the fact that aluminum chloride also acts as a cracking catalyst for such long chain alkyl aromatic hydrocarbons, and thus when such long chain alkyl aromatic hydrocarbons are utilized in the process of this invention, cracking of the alkyl group may occur. In spite of this, Condensation will take place but not necessarily with the production of the simple derivative or product which might have been desired from the reactants. Such alkylaromatic hydrocarbons are often referred to in the art as alkylate and are often produced by the alkylation of simpler aromatic hydrocarbons with olefinic polymers. sues aromatic hydrocarbons includehexylbeiizene, hexyltoluene, nonyltoluene, dodecylbenzene, dodecyltoluenaetc. As stated hereinabove, in addition to aromatic hydrocarbons, haloaromatic compounds are also utilizable in the process of the present invention to produce high yields of desired products. Typical. haloaromatic compounds utilizable as starting materials within the scope of this invention include fluorobenzene, chlorobenzene, bromobenzene, iodobenzene, ortho-chlorotoluene, metachlorotoluene, para-chlorotoluene, ortho-bromotoluene, meta-brmotoluene, para-bromotoluene, o'rtho-chloroethylbenzene, meta-chloroethylbenzene, para-chloroethylbem Zene, ortho-dichlorobenzene, para-dichlorobenzene, 1,2,4- trichlorobenzene, para-dibromobenzene, ortho-bromochlorobenzene, para-bromochlorobenzene, alpha-chloro naphthalene, beta-chloronaphthalene, alpha-bromonaphthalene, etc. As stated hereinabove, these two classes of aromatic compounds, namely, aromatic hydrocarbons, and haloaromatic compounds are particularly suitable for this further extension of the so-called Friedel-C'rafts re action. I v I From the above description, itis obvious thatnot all unmodified or naturally occurring carbohydrates are equivalent in the process of this invention. Thus, it has been found that polysaccharides are unreactive with arematic hydrocarbons or haloaromatic compounds in the process of this invention. However, it has been demonstrated and will be illustrated in the examples appended to these specifications, that both monosaccharides and disaccharides can be utilized in'the described process to produce the desired compounds. One other feature of the process ofthis invention isthat' the carbohydrate starting materials utilized are sugars. In some prior art processes which have resulted in the production of some of the compositions produced herein, the starting mate-f rials have been modified so that theycan no longer be considered to be true sugars. Therefore, as set forth hereinabove, the process of the present invention results" in a more direct and economical method for producing certain known compounds as w'ellas producing certain new and novel compositions of m atter. Thus, carbohy-i drates which are condensed with aromatic hydrocarbons and haloaromatic compounds in the process of the present invention include monosaccharides or simple sugars.

naturally occurring desoxy monos accharides, omega carboxy-monosaccharides and oligosaccharides or compound sugars. Monosaccha'ri'des or simple sugars include: dioses; trioses, tetroses, pentoses, hexoses, heptoses,

octoses, nonoses, and decosesfl Oligosaccharides or compound sugars include particularly disaccharides, and also trisaccharides, and tetrasaccharides.

Utilizable simple sugars include the diose, 'glycolaldehyde; trioses such as glyceraldehyde'and s-dihydr'oxylacetone; tetroses such as erythrose, threose, erythrulose,

and apiose; the pent oses such as arabinose, xylose, ribose,

lyxose, and ketoxylose; the hexoses such as mannose,

glucose, idose, gulose, galactose, talose, allose, fanfare fructose, sorbose, tag'atose, and psicosetheptoses such as glucoheptose', mannoheptose, galactoheptose, sedoheptose'i mannoketoheptose, glucoheptulose, "and .perseulose; octoses suchas glucooctose, mannooctose and galactO.- octose; nonose's such as glucononose, and 'mannononoses;

and decoses such as 'glucodecose. Similarly,,naturally-'occurring desoxy-derivatives of simple sugars are 'utiliza ble' in this process. These desoxyderivatives' of simple sugars are formed by the replacement of a hydroxyl group in a'' sugar with hydrogen resulting only in the elimination of one oxygen atom thereby forming a methyl or methylene nk ges} a hydr9 y y1 or hydroxylmethylene linkage had previously "ccu ri'c'dfi desoxy-pentos'es and "desox hexeses are thenios't comnronly occurri g-er such com ounds and include rha nqse (a desoxy-lrexose ruco'se' (a desoxy hexosefi rh'ddeose' (adesoxy hexose), z-des'exy-riuese (a desexymexose), and '2edesoxyfmethylpentose (a desoxy-hexose); fir-ne' 'dn ega arboxy-derivatives of simple 's'ugafs; which aresniiable nthe process of the" resent invention incl-ride tartroniese'rnialdehydeor its tautomer, hydroxypyruvic acid, a,'y-dihydroxyaceto-' acetic acid, threuronic acid, 4-keto-2,3,5-trihydroxypentanoic acid, xyluronic acid, S-keto-hexarioic acids such as" skat -allelic aci s lgeie luebafic and, S-ket'omannonic acid, s-remgmo'nic acid',"and S-He alactonic acid, urortic acids such as' glucuronic'aci uronic acid, and galacturonic -acid,;aii d" the 6keto-liept anoic acids. The simple sugars and their"oniega carboxyderivatives, as 's'ta'rtiiigm'aterialsfor the rb cess ofthisinvention, may be'representedby the followirig general formulai in which A=H' and CHgOH; integer from 1 to about 12 or so, and,B=H, fCHgOH, nacoon. As an example of the u'tility of general" formulawhen A=H, n=l, Bg -H, the compound glycolaldehyde; when A,=H, n}; 1, and B ==CH OH,-the compound is glyce'raldehyde; when A" 'H {1;1, and B=COOH, the compound is tar'tronic semialdehydaa' tautom'er of hydroxypyruvic acid; when A:="CH OH, nil, and Bf-= H, the compound is s-dihydroxyacetofie; when Af JCH OI -I, n 1, and B':CH 0H, the compound is erythrulose; when A= =ClI-I 0H, n =l, and B jCOQH, the compound is 0:,7- dihydroxya ceto acetic and; A'=I rt e2, and C fi i e's p undisf o r sepr thr qse wh n A=H, i2, and B"= COOH, the'compoiindisthreuronic acid; when ACH OH, n='2, B=CH OH, the compound is riboketose, 1r xylok;e t e; when" A CH QH, nfiland B="COOH, thecompou'nd I '4-'lg eto 2,3, -trihydroxypentanoic acidrwhenAfi, n andfB CHgQH, the compound is 'ribose, .arahifiose, xyl'ose, or iyxo e; when A= H, n 1=3, and 'B-" CH Ol-i[, a compound is xyluronic acid; when A= H QH ;n1-=3', and 'B'scflioli, the compound is psicose, fructose, sorbose, or tagatose; when A=CH OH, 11:3, and nicoon, the compound is a S-ketoIieXanoic acid; whe'n 'A&H;n;=4 and B'CHQOI-I, the'compourid'is allose, altrose', glucose, maimose, gulose, idose, galactose, or arose; when' 'A=H, n ='4,' and B='COOH, the compound is a uronic acid;- when A=CH OH, ri=4, and=B=CH OH, the compounds are he toses; and when A= jCH OH, ri "="4',a'1id"B=COOH, the compounds are 6 ketohep't'anoic acids. In any of the above formulae when the hydroxyl group is replaced'by a hydrogen atom, desoxy sugars ar'e formed as hereinabove set forth. These de'soxy sugars'are'iricludabl'e within the scope of the utilizable compounds. It should be noted however that such comporindsafe still sugars and are not desoxy sugar derivatives comprising solely polyhydroxy alcohols'the use of which has been disclosed" in the prior art. Such prior art compounds have had the oxygen atom which comprises thereducin'g function of the sugar replaced, and thus can no longer be called sugars and are not within the" scope of the disclosed process;

The utihzable 'oligosaccharides or compound sugars include disaccha'rides such as the pentose-hexose saccharides including glucoapiose; viciairos'e, and primeverose; the methyl-'pentose' hexose' saccharides including glycorhamnoside, and rutinose; and the dihexoses'siichas turanose, maltose, lactose, cellobiose, gentiobiose, meli biose, sucrose, and trehalo se Other compound sugars are represented by trisa'c'charides such as the nieth'ylpentose-hexose saccharides 'including rhainin'ose," and robi- 6 nose; *the-trihexose saccharides such as marmotriose; and the trihex'osesincludingrafiinose, melezitose, and gentianose: An 'examp'le of a suitable tetrasaccharide'is stachyose; Of the above disclosed ohgosaccharides which are operable,-the disaccharides are preferred and of the dis'accharides,'=the dihexoses are preferred.

I.n myco-pendingapplication Serial No. 360,838, filed July- 10, 1953, now Patent "2,798,098, July 2, -1957, is dis closed thereaction'of hydrocarbons with carbohydrates catalyzed by hydrogen fluoride. In this application it is shown that polysaccharides are interchangeable with monoand disaccharides. It has been found inthe process of this applicatiomhowever, that polysaccharides are inoperable. Thus, in contrast to'the above application whereincellulose'and glucose were interchangeable, in the process of this invention, cellulose is inoperable. in asimilar manner, other polysaccharides" cannot be utilized here.

Friedel-Crafts metal halides which are used in catalytic amounts in this process comprise aluminum bromide, aluminum chloride, antimony pentachloride, beryllium chloride, bismuth chloride, ferric bromide, ferric chloride, gallium trichloride; stannic bromide, stannic chloride, titanium tetrabromide, titanium tetrachloride, zinc chloride, zinc bromide, zirconium' chloride, etc. For the purposes of this specification and the appended claims; boron trifluoride is considered to be a Friedel-Crafts metal halide; These Friedel-Crafts metal halides may, in some instances, be utilized along with a promoting amount of a hydrogen halide such as hydrogen'fluoridq-hydrogen chloride, or hydrogen bromide, the halogen in the hydrogen halide preferably being the same as the halogen inthe Friedel-Crafts metal halide. Particularly preferred Friedel-Crafts metal halides comprise aluminum chloride and aluminum bromide. Furthermore, a mixture of one or" more of the Friedel-Crafts metal halides may be utilized particularly when it is desired to have the catalyst in liquid'form. Thus, a mixture of aluminum chloride and antimony pentachloride, or a mixture of aluminum chloride and stannic chloride are operable andsometimes advantageous to'use; The aluminum halide and boron trifluoride catalysts used inthe process may also be modi fied by the addition-thereto of'certain proportions of an alcohol, ether, nitrohydrocarbon, or other solvent. The alcohols and ethers' are used preferably in the amounts needed to produce monoalcohols and monoethers of these Friedel-Crafts-metal halides. 0f such catalysts, a particularly useful combination formed by mixing aluminum chloride and/or aluminum bromidewith a nitrohydrocarbon such as nitrobenzene, or a nitroparafiin such as nitromethane, nitroethane, a nitropropane, a nitrobutane, or another nitroalkane containing 5 or more'carbon atoms per 1 molecule.

This process may be carried out by slowly adding a Friedel-Crafts metal halide in the requisite catalytic amount, or amixture ofFriedel-Crafts metal halides, or a mixture ofl riedel-Crafts metal halide and, for example, a nitroparaflin to a stirred mixture of an' aromatic hydrocarbonor a haloaromatic compound and a carbohydrate chosen from the above-described classes while said stirred mixture is subjected to a reaction temperature of from about 0' to about 105 0, preferably from about room temperature to .about 100 C., the temperature being maintained by suitable cooling and/or heating means. Conversely, the carbohydrate can be added to a stirred mixture of the aromatic hydrocarbon or haloaromatic compound and Friedel-Crafts metal halide. It is sometimes desirable tocommingle the reactants and catalyst all together at a relatively low temperature such as from about C. to' about 30 C. and then to permit the reactionrnixture towarm gradually while the reactants and" catalyst are stirred by suitable mixing means such as a motor driven stirrer or other suitable mixingequipment. While the -molar quantity of aromatic compound which reacts: with a molar quantity ofmonosaccharide unit is seldom more than two, larger quantities of aromatic are often present in the reaction mixture for ease of operation. After the catalyzed reaction between the aromatic hydrocarbon or haloaromatic compound and the carbohydrate reaches the desired stage of completion, which stage can be determined usually by the suspension of hydrogen halide evolution, the used catalyst or used catalyst sludge is separated from the organic reaction product. This can be accomplished in a variety of manners. In one method, the reaction products and catalyst are allowed to separate into layers, the catalyst is removed as a lower layer, and water is added to the reaction products. The water is then neutralized, for example, by the addition of ammonium hydroxide until a pH of 7 is attained and Friedel-Crafts metal hydroxide such as aluminum hydroxide which precipitates is removed by filtration. Since both water-soluble and waterinsoluble products are formed, the resultant water-solution and wash waters and hydrocarbon layers must be concentrated and the desired products recovered therefrom by known techniques. This separation can be accomplished bv the use of different solvents in which the reaction products have varying solubilities.

The amount of Friedel-Crafts metal halide, particularly aluminum chloride, which is used as a so-called catalyst in the process of the present invention mustbe such so that at least about one molar equivalent of metal halide is utilized with respect to the amount of carbohydrate of the type hereinabove specified. Larger amounts of aluminum chloride may be used depending on the particular reaction product desired. Thus, up to 6 molar equivalents of aluminum chloride may be utilized for a pentose, 7 molar equivalents for hexose, and 8 molecular equivalents of aluminum chloride for a heptose.

I have also found it desirable. on occasion, to employ stannic chloride in the reaction system along with aluminum chloride in order to give a liquid catalyst phase. The stannic chloride per so may modify the reaction; however, its function is intended to be mainly physical.

It should be noted that these Friedel-Crafts metal halides, particularly aluminum chloride or aluminum bromide, act not only as catalysts but as reagents in the reaction. Hydrogen halides are evolved in large quantities, usually in an amount such that one mole of hydrogen halide is evolved per mole of hydroxyl groups in the starting carbohydrate. The catalyst as introduced is not recovered as such after the reaction and in this sense it may be added that these Friedel-Crafts metal halides do not simply act as catalysts in the narrow sense of the term, but act as both catalysts and reagents in the reaction.

As stated hereinabove, the organic reaction products and used catalyst sludge separate as layers which may be recovered separately, the used catalyst sludge being in a form suitable for recycling to the process. The organic reaction product or layer is then subjected to suitable washing, drying, and separation in order to recover the condensation'products formed by the reaction of the charged aromatic hydrocarbon or haloaromatic compound with the particular carbohydrate utilized. The organic reaction product may also be separated from the used catalyst by means of an organic solvent such as alcohol or an ether in which most of the organic ma terial may be dissolved. Thus, the product formed by reacting toluene with glucose in the presence of aluminum. chloride may be separated into an alcohol-soluble and water-insoluble product and into an alcohol-insoluble and water-soluble product. Furthermore, a product may also be isolated from the excess toluene utilized, this product being insoluble in both water and alcohol.

The type of product obtained in this process is dependent not only upon the chosen starting material but also upon the conditions of the reaction employed. This will be further illustrated in the examples. However, by way of example herein, in the interaction of glucose and toluene, lower temperatures, minimum amounts otcatalyst, and/or shorter contact times give higher yields of water-soluble reaction products. Conversely, improved yields of water-insoluble reaction products in the interaction of glucose and toluene is obtained at higher temperatures, with greater than minimum amounts of catalyst, and/ or longer contacttimes.

The reaction products of this process lead to materials having diversified uses. Some of these are enumerated as follows:

(a) Detergents:

(1) Sralfonale rype. -Sulfation of the products lead to compounds of the R--SO H type which can be converted into surface active salts. Further, in someinstances, compounds may be directly prepared having the R-SO H structure.

(2) Sulfate type.- -Sulfation of these products lead to compounds of the ROSO H type which, if desired, can be converted into salts.

(3) Nonionic type.The substituted products are water-soluble to diflz'erent degrees depending upon the size and nature of the substituent. Thus, for example, it is possible to make a series of surfaceactive agents with increasing hydrophobic-hydrophilic ratio in the molecule by reacting glucose with different aromatic hydrocarbon derivatives.

(4) Detergent aids.--The structure of some of the products are related to compounds found useful as detergent aids (that is, compounds which when added to a detergent in small concentrations rather markedly increase their effectiveness). They may accordingly find use in that field.

(b) Surface coatings and resins: Some of the reaction products can be used per se as surface coating materials. Resins can be made by heating many of the reaction products with formaldehyde, urea, phenoL'anili-ne, etc., and combinations of the above-enumerated compounds. A specific example of the utility of some of these reaction products is given in U.S.P. 2,722,521. For example, it is shown therein that'a resin is readily prepared by heating together one part by weight 1,1-di-ptolyl-l-desoxy-glucitol and 2.5 parts by weight of phthalic anhydride at a temperature of 200 C. to about 250 C. for a time of 20 minutes. Further specific utility is illustrated by a study of the specification of the hereinabove referred to patent.

(c) Explosives: Nitration of many of the reaction prod ucts will give explosives. These explosives will contain in some instances nitro groups attached to aromatic rings as well as being nitro-alcohol derivatives.

(d) Fermentation: The conversion of many of the reaction products into other useful chemicals such as plastics, etc. can be accomplished by employing the products as a substratuum for growing certain species of bacteria. It has been observed that water concentrations of some of these products support the growth of fungi.

(e) Pharamaceuticals: Since many of the products which can be prepared by the present process are either completely newin constitution, or hitherto unavailable in appreciable amounts and combine the chemistry of carbohydrates on one hand, and of certain aromatic compounds on the other hand, they open up a completely new field of substances adaptable for use in medicinal chemistry or in general chemical synthesis.

(f) Gelling agents: Various reaction products are efiective for gelling paraffinic or aromatic hydrocarbons. Thus, for example, a small quantity of one of the re action productsof toluene and fructose gels benzene, and pentane to a lesser, extent. I

(g) Plasticizers: It is possible to balance the hydrophobic and hydrophilic parts ofthe; molecule, going all the way from water-soluble hydrophilic materials to hydrophobic actingcompounds, wherein the hydrocarbon or aromatic derivative partpr'edominates over the oxygenated part,'-thus producing new plasticizing agents.

Examples of aryl-substit'uted desoxy-alditols prepared by. .the1PtQ ..9. .fih V 1ti9n dT19. iQ-f.= l d substituted compounds including 1-phenyl 1-desoxyglucitoL l,1 -di-phenyl-l-desoxy glucitol, l5p'-tolyl'-1- desoxy glucitol, 1,1f-di-p-tolyl;l-desoxy-glucitol; lf-(3,4- dimethylphenyl') -l-desoxy-g'l ucitol, l',1-di-(3,4-dime"thylphenyl)-l-desoxy-glucitol, l'-p'-ethylphenyl-l=desoxy glucitol, 1,1-di-p-ethylphenyl-l-desoxy-gllicitol, etc. These examples are of compounds prepared utilizing glucose as the carbohydrate reactant and similar derivatives are obtained when other aldoses' are utilized; In' asimilar manner, haloaryl-substituted 'des'oxy alditols include 1- (4-chlorophenyl)-l-desoxy-glucitol, 1,1-di-(4-chlorophenyl)-l'-desoxy-glucitol, 1-(4-bromophenyl) l desoxy-glucitol, 1','1-di-('4-bromophenyl)-1-desoxy-glucitol, etc. The production of aryl-substituted desoxy-alditols and haloaryl-substituted desoxy-alditols can be illustrated by the following equation in which glucose is utilized as the carbohydrate reactant:

sat

it-hon no-o n 11, 3

no-on (EHQOH n H H' '011 H-(L-OH Ito-041 50-41-11 n-o-on H-h-on H4 2" n-o-on $11.0 135011 I n} like mama; the re p't oh or aromatic hydrocarbons or haloa r omatic compounds:withketosesugars can be exemplified ln all of these reactionsj'either the monosubstituted m di-substituted compounds'can be obtained dependingupoh the conditions utilized; Ordinarily, howeve'tja' mxm e or both compounds is obtained. I I Thelnature or tliis invention is illustrated runner b3 thefollowing examples which, however, should not he construed to limit unduly the generally broadscope or this finventioin I I .I I II I w: 7; hese were all carriedout in a simila'r'manner. Thereactions were conducted in 'a glass alkylationiappa ratus equippedwfith: an inlet tube for, addinglhydrogen chl ride, itdesi red; a thermorneter well,- a mercury seal'ed stirrer, aiwatercooled reflux condenser. The reactciontact ed for ja speeified time while maintain ing the temperature mang r a water bath. In some of the experimen ts hydrogen chloride ga's was passed iiito the fiaslt dur ing contacting. Attheend of coili afii i thereactioninixtuife hydrolyzed with ice and cold waten -ancl any insoluble product was removed by filtra abi In each instance the aromatic reactant in near excess. over the carbohydrate. The filtratefwa's neutralized with caustic and the precipitate removed; filtration, I 1 Subsequent separations are described further in the -following examples.

v I L iii i illiistrates Ieaction of d-glu cose' and ene to reem t-one of the reaction products 1: 0 t oiii in tlie abhiie-describe'd alkylation flask. In each case, a large molar excess of benzene was utilizedg-raiig' ing from a 22:1 to 17:1 molar excess. The aluminum chloride'iwas utilizedin a: molar ratio based'up'oiiddesoxy- 'glucitoli' These experiments were carried glucose arm-"51511 o ols 1. The re ain rf'sev'agi experiments-using diife'rent conditions are summarized in the following table:

'Table'l '"fsb'l n. l Reaction of d-glucose and benzene Experiment No 2 3' 4 Charge, grams: d Glu 36 36 3s 36 Benzene-- 342 266 266 267 Anhydrous aluminumehloridem 144- 54 13 -13.- Mol ratio, Alol ld gluose 5. 5 2. 1 0. 5 0.5 Anhydrousl hydrogen chloride 1 ..(hours of addition) 0 0 0 v 17 Conditions:

Time, hours; 6 I -17 16.75 tlemp.. .C.. 50-80 67-81. 60-82 50-72 Results: Total aromatic-free prod- 60 36 111 28 not, grains.

Composition: I I Water-soluble a 4 18' 11 25 water-insoluble-r Alcohol-soluble 47 12 0 0 Benzene-soluble (other than alcohol-soluble) 9 4 3 a Greater tlian units compound, partiallyjinorganie. M.P. 167 0. b Greater than 90% 1,l-diphenyl-desoxy-D-g1ucito1.

The alcohol soluble, water-insoluble residue separated from experiments and 2, ineach instance was recrystallized Severn-times from boiling water. A compound insoluhle'in benzene was isolated. This pure compound nie'lts at 15454555 and has the following elemental analysis: calculatedfor' C H 2O -H O; C, 64.27%; H, 7.19%; found: C, 64.29%;1 1, 7.26%. The above elemental aanys s corresponds to l',l-diphenyl -l'-desoxy-D glueitol. "rhemel ing point checks with that for the same otnpojliiddisclosed in U.S.P. 2,460,803, column 6, line 19. Thus, the reaction results in the production of an ai yl desoxyf-alditoh I I Tlie waterf-soliihle"compound was isolated after evaporation of the OrigiHaI entane-WaShed filtrate and after treatment thereof with methyl Cellosolve and with 1,4-'

dioxan'. pure'compound has a melting point of l67fC. whencrystallized' from absolute methanol. The elemeiital aiia 'ly'sis for this compound crystallized from water arid'ethanol'is asfollowsz carbon, 34.28%; hydrogen, 6.01%; ash; 12.08%, The elemental analysis of the eoiiipdund crystallized from absolute methanol is as' follows; Ic'a'rlion,' 34.28%; 5.91% hydrogen; as, 13.04%. This compound, as stated above, is water soluble and'is' slightly s'iilulile in boiling ethanol, fairly soluble boiliiig me aiat'il', and dissolves in 10% caustic with a dee ening hlcdldf'ffOm water white to amber upon liea fig This'color decreases upon acidification. This compound maybe an organo metallic complex containing aluminum.

I I EXAMPLE-II This example illustrates the reacti'o'n 0f d-gluc oseand toluene. Into a glass alkylation flask as'described hereinabove was placed 264 grams of toluene, 50 grams of d-glucose, and 50 grams of aiihydrous aluminum chloride. Thus, a large'molar excess of toluene was utilized along with an aluminum chloride to glucose ratio of 1:4. Anhydrous hydrogen chloride was continuously added to the reaction mixture over a period of 4.5 hours while the temperature of the mixture was kept near 0 C. by means of an ice bath. I

After hydrolysis of the aluminum chloride, neutralization and filtration, a two phase system was obtained. This two phase system also contained a solid material.

The total product was" xt rated' several times with,

11 glucitol, melting point 155 C. This melting point checks with that given in the literature for the same compounds.

From the several pentane extracts, 3.5 grams of a high boiling liquid was separated. From this liquid there was also isolated further quantities of 1,1-di-para-tolyl-ldesoxy-D-glucitol.

EXAMPLE III This example illustrates the reaction of glucose and chlorobenzene. Thirty-six grams of d-glucose, 226 grams of chlorobenzene, and 133.4 grams of anhydrous aluminum chloride were added to the above-described alkylation flask. Again, a large excess of aromatic compound, in this case, chlorobenzene was utilized and the aluminum chloride to glucose mole ratio is 5.0:1. For the reaction, a temperature of 50-82 C. was utilized and the reactants were contacted in the presence of the catalyst for about 4 hours time.

After hydrolysis, the product was filtered under suction. By this method, 52 grams of a yellow solid was separated, melting point about 145 C.; after two recrystallizations from water a pure compound was recovered, melting at l56l57 C. A sodium fusion gave a strong test for chlorine and the compound did not show reducing properties when tested with modified Schiifs reagent. The recrystallized product, 1,1di(4-chlorophenyl)-1-desoxy-D-glucitol had the following elemental analysis: carbon, 54.07%; hydrogen, 5.49%; and chlorine, 17.90%. This analysis compares satisfactorily with that calculated for C H O Cl -H Oz carbon, 53.34%; hydrogen, 5.47%; chlorine, 17.49%. One grarn of the above pure product was oxidized with alkaline potassium permanganate and yielded 4,4'-dichlorobenzophenone, the expected oxidation product. This oxidation product was identified by its melting point of 142.5-143 C. in comparison to that given for 4,4-dichlorobenzophenone in Beilstein, volume VII, page 420, which lists the melting point of this compound as 144-145 C. The elemental analysis found for this 4,4'-dichlorobenzophenone was as follows: carbon, 62.05%; hydrogen, 3.40%; and chlorine 28.32%. This compares closely to that calculated for C H OCl which is as follower carbon, 62.18%; hydrogen, 3.21%; and chlorine, 28.24%.

The liquid portion of the reaction product consisted of a water layer and an organic layer. This liquid product was extracted with n-pentane and the more soluble solid product settled out and was removed by filtration. The pentane extract yielded two grams of an amber solid. The solid product which settled out and which was removed by filtration was a light tan solid which was dissolved in alcohol. Upon evaporation of this alcohol solution to dryness, 16 grams of an amber glass was recovered. From this amber glass additional 1,1-di-(4- chlorophenyl) -l-desoxy-D-glucitol crystallizes in the form of white needles. This new composition of matter is soluble in alcohol and slightly soluble in boiling benzene. Its structure is given as follows:

11 iQ I HOH CHOH

CHOH

HOE

HQOH

EXAMPLE IV This example illustrates the reaction of a' ketose sugar, fructose, with toluene. Four different experiments were carried out in the same manner as described hereinabove. The results of these experiments are summarized in the following table:

In experiment 5 the reaction was carried out at 0 C. for 5.5 hours with continuous hydrogen chloride addi tion. Indication of reaction was obtained from the toluene-soluble segment from which a tan solid was recovered. It was obvious, however, that these conditions were not optimum.

Experiment 6 was carried out near 40 C. by contacting the reactants for 3 hours time. As shown in the above table, the reaction product was separated, after hydrolysis, into a water-soluble segment, a toluene-soluble segment, and into a water and toluene insoluble segment. The water-soluble segment amounting to 11 grams was a soft light amber tacky product soluble in methanol and propanol and somewhat soluble in hot acetone. It was not characterized further. The toluenesoluble segment was a light amber product of a soft and tacky nature. By extraction, this toluene-soluble segment was separated into 1.5 grams of pure diaryl product which separated as white platelets from isopropyl alcohol melting at 190195 C., into about one gram of hydrocarbon melting at 200-210 C., and into five grams of undetermined product. The water and toluene insoluble product amounting to 26.7 grams yielded 21.4 grams of crude ditolyl fructitol melting at 197- 199 C. after recrystallization from alcohol. There was also 5.3 grams of undetermined product in this water and toluene insoluble material.

In a like manner in experiment 7 there was recovered 16.0 grams of ditolyl fructitol from the toluenesoluble segment and 9.5 grams from the water-insoluble toluene-insoluble segment. The same product was again isolated in experiment 8. This di-tolyl-fructitol after recrystallization from isopropyl alcohol was found to have a metling point of 199-200 C. It was also found to contain by elemental analysis 72.80% carbon and 7.84% hydrogen. These quantities are in accord with the calculated values for C H O containing 72.70% carbon and 7.93% hydrogen. Since the empirical formula by elemental analysis is C H O the compound incorporates one fructose residue with two tolyl units, having been formed with the elimination of two molecules of water. In contrast to what might have been expected, the di-tolyl fructitol from this reaction oxidizes to terephthalic acid, identified by its dimethyl ester melting at 139 C. The di-tolyl-fructitol formed a tetraacetate of melting point -112" C. This tetraacetate analyzed as 66.84% carbon and 7.07% hydrogen in comparison to the calculated values for C H O (C H 0) of 67.4% carbon and 6.8% hydrogen. Hydrogenation of this diaryl fructitol shows that only one of the aromatic nuclei is hydrogenated. The hydrogenation results in a pure product in the form of white needle crystals melting at 179181 C. The elemental analysis of the hydrogenated diaryl fructitol shows that it contains 71.27% carbon and 9.49% hydrogen in comparison to the calculated value for C H O of 71.5% carbon and 9.5% hydrogen.

j. EXAMPLE V This example illustrates the reaction of sorbose, a

a es-m 1 3 ketose' sugar, with'toluehe. Ih this eitanipfle g60 grams of toluene is contacted grams of sorbofselin the presence of 134 grams of anhydrousaluriiinum -chloride. This'reaction was carriedoiit at about 40 C. for a bout 3hours time. Here again, a la'rg'e eircessoftoluehewas utilized along with a 551" molar ratid'of aluminum chloride to sorbose. v a, y

The product was separatedjinto" ajwaterisblubie segment, a toluene-soluble segment;'and"awater andtoluene insoluble segment. From the wat er and toluene insoluble segment (amounting to' 39.3 grams) was; separated 30 grams by exhaustive eirtract'ion'with water; This substance after recrystallization from isopropyl alcohol yielded a ditolyl-sorbitol with arrielting point of" 102'- 103 C. Thepure'produ'ct iri'the form of white needle crystals was found by elemental analysis to contain 73.11% carbon and 7.93 hydrogen which values compare well with those calculated forC H O of 72.70% carbon and 7.93% hydrogen? 'di'=t olyl s'orbitiol oxidizes to yield terephthalic acid whichwas identified by the melting point of its dimethyl esterof 138. 5* f13'9.5; C; Attempts to prepare an acetate derivative yielded only a syrup-like product. i H A Fructose as utilized in Example IV and s'orbose as utilized in Example V are ketose's which differ only in the configuration of one of'thei'ri carbon atortist Thus, by reaction with' toluene they each' gave respectively a ditolyl-fructitol and a di-tolyl-sorbitol. That these compounds are not identical is plainly evident from the difierence in their melting points.

This example illustrates the reaction of a disa ccliaride, sucrose, with toluene. This example was carried out in substantially the same manner as described hereinabove. In this experiment, 260 grams of toluene was contacted with 17.3 grams of sucrose in the presence of 70 grams of aluminum chloride. This reaction was carried out at about 60 C. for 5.25 hours.

The product after hydrolysis was filtered, separating the product into a toluene and water insoluble white solid and into a filtrate composed of a light amber toluene layer and a colorless water layer. From the solid material after repeated fractional crystallizations was obtained both 1,1-di-para-tolyl-l-desoxyglucitol and also di-paratolyl-fructitol. The di-tolyl-glucitol melted at 154-155 C. after recrystallization from water and its mixed melting point with a pure sample was not depressed. The ditolyl-fructitol after recrystallization from water melted at l95-197 C. and did not depress a pure sample of the di-tolyl-fructitol obtained as shown in Example IV Thus, the reaction products obtained from sucrose, a disaccharide composed of one glucose unit and one fructose unit, are the same as compounds formed by independently reacting toluene with glucose and with fructose.

I claim as my invention:

1. A process which comprises reacting an aromatic compound selected from the group consisting of aromatic hydrocarbons and haloaromatic compounds consisting of carbon, hydrogen and nuclear halogen with a carbohydrate selected from the group consisting of monosaccharides, naturally occurring desoxymonosaccharides, omega-carboxy-monosaccharides, and oligo-saccharides in the presence of a catalytic amount of a Friedel-Crafts metal halide at reaction conditions of temperature and pressure to produce a compound selected from the group consisting of aryl-substituted desoxy-alditols, haloarylsubstituted desoxy-alditols, aryl-substituted desoxy-ketitols, and haloaryl-substituted desoXy-ketitols, and recovering said compound.

2. A process which comprises reacting an aromatic hydrocarbon with a carbohydrate selected from the group consisting of monosaccharides, naturally-occurring desoxy-monosaccharides, omega-carboxy-monosaccharides,

14 aiid oligosaccharides in the presence of a catalytic amount of a Friedel-Cra'fts metal halide at reaction seminars of temperature and pressure to produce a compound s' lected from the group consisting of aryl-subs'tituted des oXy-alditols and aryl-substituted desoXy-ketitols; and recovering said compound.

3 A process which comprises reacting a haloa'r'o'matic compound consisting of carbon, hydrogen and nuclear halogen'with a carbohydrate selected from the group eon: sisting of monosaccharides, naturally-occurring desoxy monosaccharides, omega-carboXy-monos'accharides, arid oligosaccharide's in the presence of a catalytic amount or a FriedeI-Cra'fts metal halide at reaction conditions-of temperature and pre'ssu'reto produce a compound selected from the group consisting of haloarylsubstituted de'sox'y alditols and haloaryl-substituted k'etitols, and' recovering said compound. h v

4. A pr'ocess which comprises reacting an aromatic Hy drocarbon with a carbohydrate selected from the group consisting of monosaccharides, naturally-occurring d'e'soxy monosaccharides, omega-carboxy-monosaccliarides, and oligosaccharides in the presence of a catalytic amount of aluminum chloride at' reaction conditions of temperature and pressure to produce a compound selected from the group consisting of aryl-substituted deso y-alditol's and aryl-substituted desoxy-ketitols, and recovering said compound.

5. A process which comprises reacting a haloarorn atic compound consisting of carbon, hydrogen and nuclear halogen with a carbohydrate selected from the group consisting of monosaccharides, naturally-occurring desoxy: monosaccharides, omega-carboxy-monosaccharides, and oligosaccharides in the presence of a catalytic amount of aluminum chloride at reaction conditions of temperature andpressure to produce a compound selected from theg'roup' consisting of haloaryl-substituted desoxy-alditols and haloaryl-substitutedketitols, and recovering said compound.

6. A process which comprises reacting an aromatic hydrocarbon with a carbohydrate selected from the group consisting of monosaccharides, naturally occuring desoxymonosaccharides, omega-carboxy monosaccharides, and oligosaccharides in the presence of a catalytic amount of aluminum chloride at a temperature of from about room temperature to about C., and at a pressure of from about atmospheric to about 100 pounds per square inch to produce a compound selected from the group consisting of aryl-substituted desoxy-alditols and aryl-substituted desoxy-ketitols, and recovering said compound.

7. A process which comprises reacting a haloaromatic compound consisting of carbon, hydrogen and nuclear halogen with a carboxyhydrate selected from the group consisting of monosaccharides, naturally occurring desoxymonosaccharides, omega-carboxy monosaccharides, and. oligosaccharides in the presence of a catalytic amount of aluminum chloride at a temperature of from about room temperature to about 100 C. and at a pressure of from about atmospheric to about 100 pounds per square inch to produce a compound selected from the group consisting of haloaryl-substituted desoxy-alditols and haloaryl-substituted ketitols, and recovering said compound.

8. A process which comprises reacting an aromatic hydrocarbon with a monosaccharide in the presence of a catalytic amount of aluminum chloride at a temperature of from about room temperature to about 100 C. and at a pressure of from about atmospheric to about 100 pounds per square inch to produce a compound selected from the group consisting of taryl-substituted desoxy-alditols and aryl-substituted desoxy-ketitols, and recovering said compound.

9. A process which comprises reacting an aromatic hydrocarbon with a disaccharide in the presence of a catalytic amount of aluminum chloride at a temperature of from about room temperature to about 100 and 15 at a pressure of from about atmospheric to about 100 pounds per square inch to produce a compound selected from the group consisting of aryl-substituted desoxy-alditols and aryl-substituted desoxy-ketitols, and recovering said compound.

10. A process which comprises reacting a haloaromatic compound consisting of carbon, hydrogen and nuclear halogen with a monosaccharide in the presence of a catalytic amount of aluminum chloride at a temperature of from about room temperature to about 100 C. and at a pressure of from about atmospheric to about 100 pounds per square inch to produce a compound selected from the group consisting of haloaryl-substituted desoxyalditols and haloaryl-substituted ketitols, and recovering said compound.

11. A process which comprises reacting chlorobenzene with glucose in the presence of a catalytic amount of aluminum chloride at a temperature of from about room temperature to about 100 C. and at a pressure of from atmospheric to about 100 pounds per square inch to'produce a chlorophenol desoxy-glucitol, and recovering said compound.

12. A process which comprises reacting toluene with sucrose in the presence of a catalytic amount of aluminum chloride at a temperature of from about room temperature to about 100 C. and at a pressure of from about atmospheric to about 100 pounds per square inch to produce a compound selected from the group consisting of aryl-substituted desoxy-alditols and aryl-substituted desoxy-ketitols, and recovering said compound.

13. A process which comprises reacting an aromatic hydrocarbon with a ketose in the presence of a catalytic amount of aluminum chloride at a temperature of from about room temperature to about 100 C. and at a pressure of from about atmospheric to about 100 pounds per square inch to produce an aryl-substituted desoxyketitol, and recovering said compound.

14. A process which comprises reacting toluene with fructose in the presence of a catalytic amount of aluminum chloride at a temperature of from about room temperature to about 100 C. and at a pressure of from about atmospheric to about 100 pounds per square inch to produce a para-tolyl-desoxy-fructitol, and recovering said compound.

15. A process which comprises reactin an aromatic hydrocarbon with an aldose in the presence of a catalytic amount of aluminum chloride at a temperature of from about room temperature to about 100 C. and at a pressure of from about atmospheric to about 100 pounds per square inch to produce an aryl-substituted desoxyalditol, and recovering said compound.

16. A process which comprises reacting benzene with glucose in the presence of a catalytic amount of aluminum chloride at a temperature of from about room temperature to about 100 C. and at a pressure of from about atmospheric to about 100 pounds per square inch to produce a phenyl-substituted desoxy-glucitol, and recovering said.

compound.

' 17 *A process which comprises reacting toluene with glucose in the presence of a catalytic amount of aluminum chloride at a temperature of from about room temperature to about 100 C. and at a pressure of from about atmospheric to about 100 pounds per square inch to produce para-tolyl-desoxy-glucitol, and recovering said compound.

References Cited in the file of this patent UNITED STATES PATENTS 2,252,725 Niederl Aug. 19, 1941 2,460,803 Bonner et a1. Feb. 8, 1949 2,472,276 Bonner et a1. June 7, 1949 

1. A PROCESS WHICH COMPRISES REACTING AN AROMATIC COMPOUND SELECTED FROM THE GROUP CONSISTING OF AROMATIC HYDROCARBONS AND HALOAROMATIC COMPOUNDS CONSISTING OF CARBON, HYDROGEN AND NUCLEAR HALOGEN WITH A CARBOHYDRATE SELECTED FROM THE GROUP CONSISTING OF MONOSACCHARIDES, NATURALLY OCCURING DESOXYMONOSACCHARIDES, OMEGA-CARBOXY-MONOSACCHARIDES, AND ALIGO-SACCHARIDES IN THE PRESENCE OF A CATALYTIC AMOUNT OF A FRIEDEL-CRAFTS METAL HALIDE AT REACTION CONDITIONSOF TEMPERATURE AND PRESSURE TO PRODUCE A COMPOUND SELECTED FROM THE GROUP CONSISTING OF ARYL-SUBSTITUTED DESOXY-ALDITOLS, HALOARYLSUBSTITUTED DESOXY-ALDITOLS, ARYL-SUBSTITUTED DESOXY-KETITOLS, AND HALOARYL-SUBSTITUTED DESOXY-KETITOLS, AND RECOVERING SAID COMPOUND. 